(n-alkoxycarbonyl-n-alkylcarbamoyl) dialkyl phosphono-thioates and thiolothionates

ABSTRACT

Organo-phosphonates, -phosphonothioates and phosphonothiolothionates having inter alia insecticidal, acaricidal and nematicidal activities.

United States Patent Pianka 1 Jan. 16, 1973 [54] (N-ALKOXYCARBONYL-N- [56] References Cited ALKYLCARBAMOYL) DIALKYL PHOSPHONO-Tl-IIOATES AND UNITED STATES PATENTS THIOLOTHIONATES 3,420,918 l/l969 Fancher et al ..260/938 Inventor: Max Pianka St- Albans, England 3,5I7,089 6/1970 Newallls et al. ..260/942 [73] Assignee: The Murphy Chemical Company OTHER PUBLICATIONS Lmmed Aibans England Pinka, Chemistry and Industry, March 1 l, 1961, p. 22 Filed: July 8, 1969 324 [21 1 Appl' 84o063 Primary ExaminerLewis Gotts Assistant Examiner-Anton H. Sutto [30] Foreign Application Priority Data Attorney-Bacon and Thomas July 15, 1968 Great Britain ..33,690/68 [57] ABSTRACT U-S- Cl. v R, organo phosphonates -phosphonothioates and 260/971, 260/979, 424/21 1 hosphonothiolothionates having inter alia insec- [51] Int. Cl. ..C07f 9/40, AOln 9/36 ticidal, acaricidal and nematicidal activities [58] Field of Search ..260/938, 942

17 Claims, N0 Drawings (N-ALKOXYCARBONYL-N-ALKYLCARBAMOYL) DIALKYL PHOSPHONO-THIOATES AND THIOLOTHIONATES This invention is concerned with new chemical compounds having useful insecticidal and acaricidal properties, and to preparations containing them.

According to the invention there are provided compounds of the formula:

in which R and R, which can be the same or different, are aliphatic groups having one to four carbon atoms, or aromatic groups, I

R is a hydrogen atom or an aliphatic group having one to four carbon atoms,

R is an aliphatic, preferably alkyl or alkenyl group having one to carbon atoms, and

X and Y, which can be the same or different, are oxygen or sulphur atoms.

The groups R, R, R may be saturated or unsaturated groups, e.g., alkoxyalkyl, alkyl, alkenyl, haloalkyl or alkylthioalkyl groups. Methyl and ethyl groups are particularly preferred. Other groups include propyl, isopropyl, butyl, ethoxyethyl, methoxyethyl, allyl, and 2-chloroethyl.

Where R and/or R is aromatic it may be a phenyl group or a phenyl group substituted with, for example, lower alkyl or halogen.

The group R may be a methyl, ethyl, n-propyl, 35

isopropyl, butyl, pentyl etc. group. R may be'alternatively an alkenyl, alkynyl, alkoxyalkyl, or alkylthioalkyl group.

Compounds of formula I wherein X and Y are different and the other variables are otherwise identical can of course exist in isomeric forms, the O:P.S and S:P.O forms. Reference to either form herein should be construed to refer to the other form as well.

The compounds according to the invention possess very interesting biological activity especially in comparison with organophosphate pesticides. Thus they are highly active by soil application. They are highly active against Plulella maculipennis, Sitophilus granarius (grain weevil), and against Myzus persicae. (Myzus persicae is a green sucking aphis, which infests sugar beet and potato plants and acts as a vector of virus yellow in sugar beet and various virus diseases in potato, causing a weakening of the infected plant.) Some of the compounds according to the invention are exceptionally active against spider mites (T. telarius) which are resistant to organophosphate miticides.

In general, the compounds according to the invention have better activities than the corresponding phosphates, and some of the compounds have much better activities. The compounds, while being biodegradable, in general are longer lasting than the corresponding phosphates.

S-(N-methoxycarbonyl-N-methylcarbamoylmethyl)dimethylphosphonothiolothionate was found to possess an acute oral toxicity (LD of 57 mg/kg. in rats, and a favorable ratio of insecticidal activity to mammalian toxicity.

The compounds according to the invention can be prepared by any convenient method. According to one feature of the invention, there is provided a process for the preparation of a compound of the formula I above which comprises reacting a compound of the formula.

in which R, R, X and Y are as hereinbefore defined, and Q represents a hydrogen atom, an alkali metal, ammonium, or an organic cation, with an N-haloacctylcarbamate of the formula Hal-CH -CO-NR CO R ill in which R and R are as hereinbefore defined, and Hal represents a halogen atom, i.e. chlorine, bromine, or iodine, the process being carried out in the presence of an acid binding agent when 0 represents a hydrogen atom.

Suitable acid binding agents are, for example, alkali metal carbonates such as sodium or potassium carbonate, and tertiary organic bases such as pyridine and triethylamine. The reaction may, if desired, be carried out in a solvent medium. Suitable solvents are water, ketones, e.g. acetone, methylethylketone, and methylisobutylketone, dioxan, alcohols, e.g. methanol, ethanol and isopropanol, ethers e.g. diethyl ether and diisopropyl ether, hydrocarbon solvents, e.g. petroleum ether, benzene and toluene, halogenated hydrocarbon solvents, e.g. chloroform, carbon tetrachloride, methylene dichloride and chlorobenzene, and amide and nitrile solvents, e.g., dimethylformamide, dimethylacetamide, and acetonitrile.

Preferably an alkali metal, e.g., sodium or potassium, or ammonium salt of the formula II is reacted with an N-chloroacetyl-carbamate of III.

The compounds of the formula II can be prepared according to methods described in the literature, for example according to Chupp and Newallis, J. Org. Chem., I962) 27, p. 3832, British Patent Specification No. 912,747 and Hoffmann, Kagan and Carfield, J.A.C.S., (1959) 8l,p. 148.

According to a further feature of the invention, there is provided a process for the preparation of compounds of the formula I (hereinbefore defined) in which X and Y both represent sulphur atoms which comprises reacting a compound of the formula in which R is as hereinbefore defined with an N- haloacetyl-carbamate of the formula III above in the presence of an alcohol ROH (in which R is as hereinbefore defined) and an acid binding agent.

The reaction is preferably effected in the presence of a solvent, which is conveniently an excess of the alcohol ROH.

The acid binding agent is preferably an alkali metal carbonate, such as sodium or potassium carbonate, or a tertiary organic base, such as pyridine or triethylamine.

Generally, it will be convenient to effect the reaction according to the invention at or around ambient temperature. If desired temperatures ranging from to 100 C may be used care being taken to prevent decomposition or rearrangement of the reactants or final product.

The compounds according to the invention can be formulated for use in any desired way. Generally such formulations will include the pesticidal compound or toxicant in association with a suitable carrier or diluent. Such carriers may be liquid or solid and designed to aid the application of the toxicant either by way of dispersing it wherein it is applied or to provide a formulation which can be made by the user into a dispersible preparation.

Liquid preparations thus include preparations of the toxicant in the form of solutions or emulsions which can be used on their own or be adapted to be made up with water or other diluents to form sprays etc; in such cases the carrier is a solvent or emulsion base nonphytotoxic under the condition of use. Generally such preparations will include a wetting, dispersing or emulsifying agent. Other liquid preparations include aerosols in which the toxicant is in association with a liquid carrier or propellant.

Solid preparations include dusts and wettable powders, granulates and pellets, and semi-solid preparations such as pastes. Such preparations may include inert solid or liquid diluents such as clays, which may themselves have wetting properties, and/or wetting, dispersing or emulsifying agents; binding and/or adhesive agents may also be included. Solid preparations also include thermal fumigating compositions wherein the toxicant is associated with a solid pyrotechnic component.

The compounds according to the invention may be used, if desired, in admixture with compatible insecticides and/or fungicides. v

For the better understanding of the invention, the following examples are given by way of illustration only. In these examples temperatures are given in degrees centigrade, and parts, unless otherwise stated are by weight. Where parts by weight and parts by volume are mentioned together these are to be taken as having the relationship of grams to ccs.

EXAMPLE 1 S-(N-Methoxycarbonyl-N-methylcarbamoylmethyl) dimethylphosphonothiolothionate Potassium dimethylphosphonothiolothionate (30 g., 0.165 mole, m.p. 180), in acetone (140 ml.), was added to a solution of methyl N-chloroacetyl-N- methyl-carbamate (24.9 g., 0.15 mole) in acetone (40 ml.). The reaction was slightly exothermic. The reaction mixture was left to stand at room temperature for 1 day, potassium chloride (11.2 g.. theory 11.21 g.) was filtered off, and the filtrate distilled at 10 20 mm. on a steam-bath. The residue was dissolved in ether and washed with water. The ether solution was dried (Na SO and distilled at 0.8 mm. at room temperature to leave a white oil (38.95 g., 95.9%), n 1.5485 (Found: N, 5.3; P, 11.25; s, 23.6. C H NPO S requires N, 5.16; P, 11.44; S, 23.6%). It distilled at 172-174/2.5 mm., n 1.5475.

EXAMPLE 2 S-(N-Methoxycarbonyl-N-methylcarbamoylmethyl qi l xlshsyhsqq hiol b a s cHii -s s- I-CH; omon NazCO;

+ Cl.CH2.GO.N(CH ).C02.CH3

S=P--S.CHz.C0.N(CH;).COz.CH;

Methyl thionophosphine sulphide (11.0 g., 0.01 mole), prepared by the method of PE. Newallis, J.P. Chupp, and LCD. Groenweghe, J. Org. Chem., (1962) 27, 3829, was allowed to dissolve in methanol (30 ml.) (this reaction is exothermic). To the resulting solution was added anhydrous sodium carbonate (5.3 g., 0.1 equiv.). There was a vigorous evolution of carbon dioxide. A solution of methyl N-chloroacetyl-N- methyl-carbamate (15.7 g., 0.095 mole), in acetone (20 ml.), was added and the mixture refluxed for 30 min. The precipitated solid was filtered off and the filtrate refluxed for a further 30 min. There was no further precipitation of solid. The methanol and acetone were distilled off and the residue was dissolved in ether and washed with 0.5N sodium carbonate solution and then with water. The ether solution was separated and dried (Na SO The dried solution was distilled at 2 mm. and room temperature to leave a yellow oil (24.05 g., 93.4%), n l.5460.

EXAMPLE 3 S-(N-Methoxycarbonyl-N-methylcarbamoylmethyl) 0- methyl ethylphosphonothiolothionate This compound, which was prepared by the method of Example 1 except that potassium O-methyl ethylphosphonothiolothionate was used, distilled at 151/0.65 mm., n 1.5438 (Found: S, 22.3. C H NO PS requires S, 22.45%).

EXAMPLE 4 S-(N-Ethoxycarbonyl-N-methylcarbamoylmethyl) methyl ethylphosphonothiolothionate EXAMPLE 5 S-(N-Ethoxycarbonyl-N-methylcarbamoylmethyl) O- ethyl methylphosphonothiolothionate OC H This compound, which was prepared by the method of Example 4 except that potassium O-ethyl methylphosphonothiolothionate was used, distilled at 138 l39/0.25 mm., n 1.5300 (Found: S, 21.3. C,,H,,,NO.,PS requires S, 21.4%)

EXAMPLE 6 S-( N-Ethoxycarbonyl-N-methylcarbamoylmethyl) diethyl phosphonothiolothionate This compound, which was prepared by the method of Example 4 except that potassium diethylphosphonothiolothionate was used and the mixture was refluxed for 4 hours, distilled at 145 146/O.35 mm., n 1.5270 (Found: S, 20.47. C H NO,PS requires S, 20.45%).

EXAMPLE 7 S-(N-Ethxycarbonyl-N-ethylcarbamoylmethyl) diethyl phosphonothiolothionate This compound, which was prepared by the method of Example 6 except that ethyl N-chloroacetyl-N-ethylcarbamate was used, distilled at 144/0.25 mm., m," 1.5215 (Found: S, 19.8. C ll- M038 requires S, 19.6%).

EXAMPLE 8 S-( N-Methoxycarbonyl-carbamoylmethyl) phosphonothiolothionate dimethyl OCH:

OCH:

S: -S-CHz-C O-NH-C 02- H:

This compound was prepared from potassium dimethyl phosphonothiolothionate and methyl N- chloroacetyl-carbamate using the conditions described in Example 1. To the oil obtained after the acetone was removed ether was added, then water, then chloroform. The aqueous layer was separated off and the chloroform solution was dried over sodium sulphate. On removal of the chloroform a solid remained. The compound was obtained as white plates, m.p. 108.5 l09.5(from toluene) Found: P, 12.0. C,,H, NO,,PS requires P, 12.0%).

EXAMPLE 9 (N-Methoxycarbonyl-N-methylcarbamoylmethyl) dimethylphosphonothioate Potassium dimethylphosphonothioate (6.9 g., 0.042 mole), in acetone ml.), was mixed with methyl N chloro-acetyl-N-methyl-carbamate (6.62 g., 0.04 mole), in acetone (10 ml.). The mixture was allowed to stand at room temperature for 3 days. The solid (2.97 g., theory for potassium chloride 2.98 g.) was filtered off and the filtrate was heated at 10 20 mm. on a steam bath. The residue was dissolved in chloroform and washed with a little water. The chloroform solution was separated, dried (M1 50 and heated at 20/ 2 mm. to leave a brown oil (9.6 g.) which was distilled. The compound boiled at 144 l46/0.5 mm., n 1.5080 (Found: S, 12.1. C H NO PS requires S, 12.55%).

EXAMPLE 10 EXAMPLE l1 (N-Ethoxycarbonyl-N-methylcarbamoy1methy1) methyl ethylphosphonothioate This compound, which was prepared by the method of Example 1 except that potassium O-methyl ethylphosphonothioute and ethyl N-chloroacctyl-N- methyl-carbamate were used, distilled at 140/0.25 mm., m, 1.4990 (Found: S, 11.3. C H NO PS requires S, 11.3%).

EXAMPLE 12 (N-Methoxycarbonyl-N-methylcarbamoylmethyl) diethyl phosphonothioate Methyl N-chloroacetyl-N-methyl-carbamate (20.7 g., 0.125 mole), in acetone (50 ml.), was added to a solution of potassium O-ethyl ethylphosphonothioate (24.0 g., 0.125 mole), in acetone (200 ml.). There was immediate precipitation of potassium chloride. The mixture was refluxed for 4% hr. on a steam bath and filtered. The acetone was distilled off at 50 60 under reduced pressure, and the residual oil dissolved in benzene (100 ml.). The benzene solution was washed with 2N sodium carbonate (20 ml.), then 1 percent sodium chloride solution (20 ml.), dried over anhydrous sodium sulphate, and the benzene distilled off under reduced pressure at 50 60. The residual oil weighed 33.2 g. (94 percent yield). lt distilled at 140 o.3 mm., n 1.4985 (Found: 5, 11.3. c,,H,.,1-1o PS requires S, 11.3%).

EXAMPLE l3 (N-Ethoxycarbonyl-N-methylcarbamoylmethyl) diethylphosphonothioate This compound, which was prepared by the method of Example 1 except that potassium diethylphosphonothioate and ethyl N-chloroacetyl-N- methyl-carbamate were used, distilled at l42/0.3 mm., m, 1.4930 (Found: S, 10.76. C, H NO PS requires S, 10.77%).

The following compounds were prepared according to the method of Example 1, using the appropriate starting materials:

Example number Formulation The products of the Examples were formulated as emulsifiable concentrates in several ways, viz:

I. 4 parts of the toxicant were mixed with I parts of Lissapol NX (a polyethylene glycol ether) and made up to I00 parts by volume with acetone.

2. 25 parts of the toxicant, 4 parts of the calcium salt of dodecyl benzene sulphonate and 4 parts of a nonionic emulsifier were made up to 100 parts by volume with heavy naphtha.

5 g of the toxicant was suspended in 7g of diacetone alcohol, and this was intimately mixed with 87 g of Ful- Iers Earth granules having a diameter between 353 and 840 microns. The granules could be applied directly to the soil.

Biological results Test of systemic activity against aphis by soil application The formulation of the toxicant as an emulsifiable concentrate was diluted with water to give 500 ppm of the toxicant. ml. of this solution was pipetted on to the soil around the base of broad bean plants growing in a 7.5cm pot.The plant was infested with Aphis fabae and assessment of the kill was made 48 hours after infestation. In this case the plants were infested directly after the application of the toxicant and counted 2 days later. Another set of plants was infested 3 days after treatment with the toxicant and counted 48 hours later. Yet another set was infested 5 days after treatment with the toxicant and counted 48 hours later. The results are shown in Table 1.

Further tests for systemic activity against aphids 1. Control of black and green aphid on rice plants The active ingredient (compound of Examples 1 and 2) was applied as a soil drench, in the form of an emulsifiable concentrate. The results were as follows:

% control 95% in 24 hours 100% in 48 hours Reinfested 1 week after treatment 90% control in 24 hours. 90% in 24 hours 98% in 48 hours 100% in 6 days Rate of application (kg/ha) 2. Control of green aphid on tobacco plants The compound of Examples 1 and 2 was applied as a 20 granular formulation which was raked into the sandy loam soil. The results were as follows:

Rate of application (kg/ha) control after 5 weeks The plants were reinfested with aphids throughout the test. There was no phytotoxicity to the tobacco plants.

3. Control of green aphid on cotton plants 35 were as follows:

Rate of application (kg/ha) No. of live aphids/per plant after 6 20 days 2.24 30 8 0 I I.I2 3 2l 0 I 0.84 47 30 3 4 phorate 2.24 I2 25 24 9 phorate I.I2 I05 60 95 Untreated control I25 80 I25 TABLE 1.APHIS FABAE SYSTEMIC 'I EST Percent control with Percent control olter dnnelox Compound of Rate of Rate of example number application 2 days 5 days 7 (lays application 2 (lays 5 days 7 days 1 and 2 500 p.p.m II? 100 100 500 ppm"... 08 100 56 1 and 2 250 p.p.n1 100 100 99 250 p.p.n1 0!) l4 0 3 500 p.p.m 100 100 100 4. 250 p.p.n1 05 I00 5. 250 p.p.m *07 .11 0. 500p.p.1n. 03 I00 00 500 p.p.1n )8 5b 0 250 p.p.1n 08 00 07 .250 p.p.n1 III] 48 0 7. 250 p.p.n1 05 00 I7 8.. 250 p.p.n1 00 08 N 0 260 1.0m I00 I00 I7 .25( p.p.ni I0... 250p.p.1n.. I00 I00 I00 .350 w.p.m II J50 p. |.|n... .10 02 0| .150 p.010, I00 7'. 28 I12. .250 p. ).n| I00 I00 I00 260 p. |.m 00 II 0 I. l00 r.n1 I00 00 I00 I00 p.p.1n .1 0 I00 III 250 I.]).n1 00 I00 I00 .250 |.p.n| 53 l 0 I4 250 p.|).|n H5 I00 [00 J50 [LILIII HS .10 3 Hi 250 i.p.1n .10 I00 I0 13hII 1.p.m Ii); .30 it I0 .250 |.|n. 03 I00 70 .560 .||.m IIH .30 II I7... 250 p. i.|n. 81' I00 )0 .550 p.|l.|n 5H '10 It In 250 r.p.n1 "20 I00 57 .250 ILILIII. .17 33 1 2| .250 11.1).01 00 00 I: .250 |.n| 07 72 I 250 ]).]).III I00 I00 07 250 .p.n| J7 33 -I 250 p.p.1n.. I00 I00 I00 250 01. 00 00 27 100 |l.]I.ll| I00 I00 I00 .250 |).|I.III 07 07 en 100 .p.n| I00 I00 I00 .500 ]).|).III 07 07 0b 250 .p.m 1m I00 00 .560 [1. mm it 3-1 I'.! 3.30 kta/hn. 80 I00 I00 3.30 kI.{./lI1I,. 0 H m 33... 25000111, .III 00 74-1 .I3I) a. |.||l 07 7'. l 34.. .H. 250 p.p.n| I 100 I00 25000111. IT 0T 57 Slow noting compounds.

The plants were reinfested with aphids throughout the test. There was no phytotoxicity to the cotton plants.

Test for activity against Aphis fabae by contact application The host plant was again the broad bean, Vicia faba. A formulation of the toxicant was diluted with water to give concentrations of toxicant of I00, 30, I0, 3 and I ppm and was applied to the plants by a dipping technique. The percentage control of aphids was assessed 48 hours after treatment. For comparison purposes, parallel tests were run using 'y-benzene hexachloride.

The results are shown in Table 2.

TABLE 2 APHIS FABAE CONTACT TEST Compound control control with of Gamma-BHC Example I 30 I0 3 1 I00 30 PP PP PP PP'" PP'" PP' PP' PP" l and 2 99+99 96 4l 3 99 65 45 3 I00 99 94 61 I6 4 83 2I 3l 5 72 48 7 6 I00 I00 I00 70 68 7 98 89 65 9 99 60 59 I0 I00 99 62 II 99 70 49 I2 I00 I00 I00 I00 67 I3 I00 I00 89 92 50 9I 34 I2 I4 I00 83 37 91 34 l2 I5 I00 99 86 91 34 I2 I6 I00 96 53 9I 34 12 I7 I00 84 26 96 63 4 I8 I00 I00 9] 9I 34 I2 I9 99 89 95 91 34 I2 99 98 89 9l 34 I2 22 I00 I00 88 98 I4 4 23 I00 I00 93 91 34 I2 24 99 I00 99 98 I4 4 25 I00 96 98 I4 4 26 I00 I00 97 99 33 6 27 I00 99 99 99 60 9 28 I00 I00 I00 99 70 99 60 9 29 I00 I00 99 82 34 6 30 I00 I00 94 I00 95 I5 31 I00 I00 I00 I00 I00 65 33 I00 I00 93 98 I4 4 34 I00 I00 99 98 I4 4 39 98 66 7O 99 33 6 Test for activity against Myzus persicae by contact application The M yzus persicae used were resistant to dimethoate. A formulation of the toxicant was diluted with water to give concentrations of toxicant of I00, 30, I0, 3 and 1 ppm and was applied to the plants (rape: Brassica napus) by a dipping technique. The percentage control was assessed after 24 hours. y-Benzene hexachloride was again employed for comparison purposes.

The results are shown in Table 3, which also includes results for demeton-methyl, dimethoate and malathion.

TABLE 3 MYZUS PERSICAE CONTACT TEST Compound of control control with Example Gamma-BHC No. 100 30 I0 3 I I00 30 I0 PP PP pp pp pp PP pp PP I and 2 I00 I00 58 I00 73 9 6 I00 I00 I00 50 25 I00 87 22 I2 I00 I00 57 2I I00 I00 44 I00 46 I8 22 I00 I00 79 I00 46 I8 24 I00 I00 96 I00 46 I8 25 I00 I00 100 I00 46 I8 26 I00 I00 I00 I00 73 9 27 I00 I00 I00 94 44 I00 73 9 28 I00 I00 6 I00 73 9 29 I00 I00 I00 I00 73 9 31 I00 I00 50 I00 85 32 I00 I00 97 7 I00 46 18 34 I00 I00 I00 50 25 I00 87 22 Demetonmethyl I00 24 5 Dimetho' 69 ate Malath- 2 ion Test for persistance of systemic activity against Myzus persicae The toxicant was applied to the soil in an aqueous dispersion at a concentration of 250 ppm. The host plant was chinese cabbage. M.persicae was placed on the plants I and 30 days after treatment. For comparison purposes a parallel test was conducted with dimefox. The results are shown in Table 4.

TABLE 4 MYZUS PERSICAE SOIL PERSISTENCY TEST control days after treatment Treatment (compound) 30 Dimefox 99 7 Examples l and 2 97 76 Example 6 91 95 Example 7 Example I2 100 Example 18 I00 Example 44 I00 Garden tests for activity against aphids I. Sugar beet plants were sprayed with an aqueous dispersion of the toxicant containing 200 ppm of the toxicant. The total number of aphids on 6 plants was counted after 5 days and 18 days. The results were as follows:

Compound Total no. of aphids on 6 plants after 5 days I8 days Examples I and 2 2 2 Example l2 0 0 Demeton-methyl 0 29 Untreated control 39 57 3. The compound of Examples 1 and 2 was tested against Rhopalosiphum insertum(pre-blssom aphis on fruit trees); it was employed in a pre-bud break application in an aqueous dispersion at 200 ppm. A test with dimethoate was conducted as a comparison. The results were assessed and 26 days after treatment, and were as follows:

Compound buds infested pre-trcatment post treatment 5 days 26 days Examples l and 2 79 7 35 Dimethoate 88 40 94 Untreated control 86 90 95 Test for activity against Tetranychus telarius by contact application Both schradan-resistant and non-resistant strains of Tetranychus telarius (red spider) were employed, the host plant being dwarf beans.

The toxicant was applied as an aqueous dispersion by a dipping technique, at concentrations of I00, 30 and ppm. The percentage control effected by each treatment was assessed after 48 hours. Comparative tests were conducted with mecarbam and parathion. The results are shown in Table 5.

TABLE 5 TETRANYCHUS TELARIUS contact test Compound of control of noncontrol of resistant Example resistant spider spider No. 100 30 I0 I00 30 I0 PP PP PP PP PP PP I and 2 I00 99 98 I00 I00 94 5 I00 I00 I00 82 78 6 I00 I00 93 I00 84 44 7 I00 I00 lOO 98 99 65 9 I00 99 I00 I00 98 93 I0 I00 I00 98 I00 92 I I I00 91 91 95 77 52 I2 I00 I00 96 I00 98 87 I5 I00 I00 99 99 89 28 I00 I00 92 I00 93 85 Mecarbam 93 86 62 Parath- 78 ion In a further series of similar tests designed to compare the activity by contact application of the compound of Examples 1 and 2 with that of known insecticides, the following results were obtained (Table 6):

TABLE 6 TETRANYCHUS TELARIUS CONTACT TEST (%) Control at p.p.m.

Non-resistant spider Resistant spider I00 30 I I00 30 I0 Compound of Examples l and 2 I00 96 93 I00 I00 94 Azinphos-methyl I00 95 95 80 58 44 Demeton-methyl I00 98 97 59 60 44 Dimethoate 61 43 42 Malathion 95 95 43 47 32 25 Mecarbam I 00 96 96 94 63 22 Plrathlon 9 I 89 67 43 9 Phenkapton Schradan Test for systemic activity against Tetranychus telarius A non-resistant strain of Tetranychus telarius was employed; the host plant was the dwarf bean. The plants were infested, and 24 hours later the toxicant was applied to the soil at concentrations of 300, I00, 30 and I0 ppm. The percentage control was assessed 48 hours after treatment. The results were as follows:

Compound control at 300 I00 30 10 ppm Example I5 I00 93 68 Dimefox 97 90 65 I9 Test for activity against Plutella maculipenm's by contact application TABLE 7 PLUTELLA MACULIPENNIS CONTACT TEST Compound of control control with DDT Example No. I00 30 I0 I00 30 10 PP" PP'" PP PP PP'" PP" I and 2 100 I00 3 I00 I00 28 4 I00 89 5 5 I00 I00 70 6 I00 28 7 90 I00 65 9 94 89 63 I0 I00 82 43 I3 98 75 64 I7 95 I00 95 89 I8 I00 I00 I00 I00 I00 80 I9 I00 I00 85 89 20 I00 I00 I00 I00 I00 80 25 I00 94 I0 95 26 33 I00 I00 28 95 26 Tests for activity against Coleoptera by contact application Three species of Coleoptera-sitophilus granarius, Phaedon cochleariae (mustard beetle adults) and Tribolium were treated with compounds according to the invention at concentrations of 300, I00 and 30 ppm. The toxicant was applied by micrometer syringe. The percentage control was assessed I week after treatment in the case of S.granarius and 30 days after treatment in the case of P.Cochleariae and Tribolium. Parallel tests were conducted with mecarbam. The results as shown in Table 8 TABLE 8 TESTS AGAINST COLEOPTERA I. SITOPHILUS GRANARI US Compound of control control with mecarbam Example I and 2 I00 92 I2 I00 76 3 I00 4 I00 5 I00 6 I00 I00 88 I00 76 l 1 I l00 96 I00 48 13 I00 100 7l 100 33 2. PHAEDON COCHLEARIAE compound control with of control mecarbam Example No. 300 I00 30 10 I00 30 PP PP PP PP" PP' PP l and 2 I00 l00 20 l0 50 70 5 100 50 50 0 6 I00 100 50 0 9 l00 100 l0 l00 I00 12 I00 100 I00 I00 30 I3 l00 100 40 60 l0 21 100 70 60 40 27 100 I00 l00 90 20 0 29 l00 l00 70 20 0 3. TRIBOLIUM Compound of control control with mecarbam Example No. 300 100 30 300 100 PP" PP PP PP PP l and 2 100 88 0 72 64 3 96 76 l6 72 64 4 96 84 24 72 64 6 92 80 64 72 64 9 100 l00 88 68 60 I3 100 80 0 48 36 l5 92 84 72 48 20 17 I00 52 0 64 40 27 100 100 56 48 28 Tests for activity against Musca domestica (house fly) by contact application The toxicant was applied by micrometer syringe (topical application) at concentrations of 300, l00, 30 and 10 ppm. The percentage control was assessed 48 hours after treatment. The results are shown in Table 9, including the results of parallel tests conducted with mecarbam.

TABLE 9 MUSCA DOMESTIC/1 CONTACT TEST Compoundof control with Test for activity against Dysdercus by contact application The toxicant was applied to Dysdercus intermedius adults by micrometer syringe, at concentration of 100, 30 and lOppm. The percentage control was assessed after 3 days. Parallel tests were conducted with mecarbam. The results are shown in Table 10.

TABLE 10 DYSDERCUS CONTACT TEST Compound of control control with mecarbam Example No. 100 30 10 1000 300 PP' PP' PP' PP" pp 1 and 2 44 mo 6 44 100 I3 lOO 100 89 I00 I00 90 27 I00 90 50 Test for activity against Agriotes TABLE 1 l WIREWORM (AGRIOTES) TEST Compound of control with Example No. control at Sppm Gamma-BHC at Sppm 6 87.5 7 100 87.5 17 I00 87.5 l8 l00 87.5 29 lOO 87.5

Test for activity against Pieris brassicae by contact application The toxicant prepared in Example 6 was applied to cabbage caterpillar (P.brassicae) at a concentration of 250ppm. For comparison purposes, carbaryl at 375 ppm was employed in a parallel test. The number of caterpillars surviving was assessed 3 days after treatment.

Treatment Mean no.0f caterpillars at 3 days Compound of Example 6 at 250ppm 2.5 Carbaryl at 375ppm 10.5 Untreated (control) 66.75

Test for activity against nematodes The activity of the compound of Examples l and 2 was tested against root knot nematodes. The host plants were tobacco and tomato. The toxicant was formulated in two ways as granules of Fullers earth on which the toxicant, dissolved in diacetone alcohol, was absorbed, and as a corn cob formulation. The formulation of the toxicant was raked into the soil before planting. Except where indicated in the following table, a two week waiting period was allowed before planting. The results were as follows, the Root knot Index being related to a scale on which 0 indicates complete control of nematodes and 5 indicates no control.

Concentration of active ingredient (kg/ha) Formulation Root Knot lndex 28 Granules 0.5 22.4 0.0 1 L2 0.05 8.96 0.8 22.4 Corn Cob 0.05 l 1.2 0.0 8.96 0.26 4.48 0.9 8.96 0.7 4.48 0.9

no waiting period.

The compound was safe to tobacco plants at 8.96 and 4.48 kg/ha but caused slight tip burn to tomato plants. However, the tomato plants had good size, color and root development. The compound also gave control of aphids on the plants by systemic action.

Further laboratory tests for insecticidal activity The following test insects were used: Boophilus decoloratus the blue tick of testing, as follows:

Hoop/rilus decolaratus blue tick larvae, are held for 24 hours in close contact with a 0.1 percent solution of the substance under test, absorbed on filter paper, after which time mortality is assessed.

10 Two tests are carried out against Lucilia sericata,

both using lst instar larvae. In one, an in vitro method, larvae are exposed to a 0.1 percent solution, absorbed on cotton wool rolls, and given horse serum for food,

assessment being after 24 hours. The second method entails inducing a flystrike on guinea pigs which are then dosed orally with the compound. Systemic activity is assessed by noting the time taken to repel larvae from the strike.

Compounds are screened against immature Aedes aegypti; 3rd 4th instar larvae in water are treated with ppm for 24 hours.

Female house flies, (Musca domestica,) are used,

(the males are more susceptible). These are dosed topically with 1 p1 of a 0.1 percent solution. Mortality is assessed after 24 hours.

The results of testing a variety of the compounds of the invention on the four above-mentioned insects are shown in Table 12.

TABLE 12 Compound Example No.

Aedes Adults LD Aedes larvae LD Musca Boophilus Lucilia larvae larvae LD LD,

0.07ppm (0.003%

0.l6ppm (0.00l%

(0.0008% (0.002% 0.17% 0.22ppm 0.003% (0.002%

0.04% 0.004% 0.07% 0.32ppm 0.01%

0.06ppm 0.004%

Good control of cabbage rootfly (Hylemyia brassicae) was obtained when the cabbage plants were treated with granules containing 5 percent of the compound of Example 17 or Example 18, used at the rate Examples 6 and 12 also gave good control of cabbage rootfly.

I claim: 1. A compound selected from the group consisting of compounds of the formula wherein R and R are lower alkyl or lower alkenyl;

R is hydrogen or lower alkyl;

R is lower alkyl; and

X and Y are sulfur or oxygen.

2. The compound of claim 1 in which R, R, and R are selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl, s-butyl, and allyl.

3. The compound of claim 1 wherein R is methyl or ethyl;

R is methyl, ethyl, n-propyl, or allyl;

R is hydrogen, methyl, or ethyl, and

R is methyl or ethyl.

4. Compounds as claimed in claim 1 in which R, R, R and R are chosen from the group consisting of methyl and ethyl.

5. Compounds as claimed in claim 1 in which X and Y are both sulphur atoms.

6. Compounds as claimed in claim 1 wherein said compound is S-(N-methoxycarbonyl-N-methylcarbamoylmethyl) dimethylphosphonothiolothionate.

7. Compounds as claimed in claim 1 wherein said compound is S-(N-methoxycarbonyl-N-methylcarbamoylmethyl) O-methyl ethylphosphonothiolothionate.

8. Compounds as claimed in claim 1 wherein said compound is S-(N-ethoxycarbonyl-N-methylcarbamoylmethyl) O-methyl ethylphosphonothiolothionate.

9. Compounds as claimed in claim 1 wherein said compound is S-(N-ethoxycarbonyl-N-methylcarbamoylmethyl) O-ethyl methylphosphonothiolothionate.

l0. Compounds as claimed in claim 1 wherein said compound is S-(N-ethoxycarbonyl-N-methylcarbamolymethyl)diethyl-phosphonothiolothionate.

ll. Compounds as claimed in claim 1 wherein said compound is S-(N-methoxycarbonyl-carbamoylmethyl) dimethylphosphonothiolothionate.

12. Compounds as claimed in claim 1 wherein said compound is S-(N-methoxycarbonyl-N-methylcarbamoyl-methyl) O-propyl ethylphosphonothiolothionate.

l3. Compounds as claimed in claim 1 wherein said compound is (N-methoxycarbonyl-N-methylcarbamoylmethyl) O-ethyl methylphosphonothioate.

l4. Compounds as claimed in claim 1 wherein said compound is S-(N-methoxycarbonyl-carbamoylmethyl) 0-propyl methylphosphonothiolothionate.

l5. Compounds as claimed in claim 1 wherein said compound is S-(N-methoxycarbonyl-N-methylcarbamoylmethyl) O-propyl methylphosphonothiolothionate.

l6. Compounds as claimed in claim 1 wherein said compound is S-(N-methoxycarbonyl-N-methylcarbamoylmethyl) diethylphosphonothiolothionate.

17. Compounds as claimed in claim 1 wherein said compound is S-(N-Methoxy carbonyl-carbamoylmethyl) O-ethyl methylphosphonothiolothionate. 

2. The compound of claim 1 in which R, R1, and R2 are selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl, s-butyl, and allyl.
 3. The compound of claim 1 wherein R is methyl or ethyl; R1 is methyl, ethyl, n-propyl, or allyl; R2 is hydrogen, methyl, or ethyl, and R3 is methyl or ethyl.
 4. Compounds as claimed in claim 1 in which R, R1, R2 and R3 are chosen from the group consisting of methyl and ethyl.
 5. Compounds as claimed in claim 1 in which X and Y are both sulphur atoms.
 6. Compounds as claimed in claim 1 wherein said compound is S-(N-methoxycarbonyl-N-methylcarbamoylmethyl) dimethylphosphonothiolothionate.
 7. Compounds as claimed in claim 1 wherein said compound is S-(N-methoxycarbonyl-N-methylcarbamoylmethyl) O-methyl ethylphosphonothiolothionate.
 8. Compounds as claimed in claim 1 wherein said compound is S-(N-ethoxycarbonyl-N-methylcarbamoylmethyl) O-methyl ethylphosphonothiolothionate.
 9. Compounds as claimed in claim 1 wherein said compound is S-(N-ethoxycarbonyl-N-methylcarbamoylmethyl) O-ethyl methylphosphonothiolothionate.
 10. Compounds as claimed in claim 1 wherein said compound is S-(N-ethoxycarbonyl-N-methylcarbamolymethyl)diethyl-phosphonothiolothionate.
 11. Compounds as claimed in claim 1 wherein said compound is S-(N-methoxycarbonyl-carbamoylmethyl) dimethylphosphonothiolothionate.
 12. Compounds as claimed in claim 1 wherein said compound is S-(N-methoxycarbonyl-N-methylcarbamoyl-methyl) O-propyl ethylphosphonothiolothionate.
 13. Compounds as claimed in claim 1 wherein said compound is (N-methoxycarbonyl-N-methylcarbamoylmethyl) O-ethyl methylphosphonothioate.
 14. Compounds as claimed in claim 1 wherein said compound is S-(N-methoxycarbonyl-carbamoylmethyl) O-propyl methylphosphonothiolothionate.
 15. Compounds as claimed in claim 1 wherein said compound is S-(N-methoxycarbonyl-N-methylcarbamoylmethyl) O-propyl methylphosphonothiolothionate.
 16. Compounds as claimed in claim 1 wherein said compound is S-(N-methoxycarbonyl-N-methylcarbamoylmethyl) diethylphosphonothiolothionate.
 17. Compounds as claimed in claim 1 wherein said compound is S-(N-Methoxy carbonyl-carbamoylmethyl) O-ethyl methylphosphonothiolothionate. 